The rovibrational spectrum assigned to the low-lying B-3(2) electronic state of ozone is measured with intracavity laser absorption spectroscopy. The experimental results are interpreted by means of quantum dynamical calculations on a global ab initio potential energy surface. The observed spectrum is shown to originate from the vibrational ground state in the local minimum of the B-3(2) potential. The spectrum of short-lived resonance states in this local minimum is analyzed. Additionally, the global minimum of the surface is shown to lie in the dissociation channel in the van der Waals region. This region supports a short sequence of weakly bound vibrational states. (C) 2004 American Institute of Physics.